Disazo dyestuffs containing phthalimide groups



United States Patent "ic 3,509,122

Patented Apr. 28, 1970 3,509,122 DISAZO DYESTUFFS CONTAINING CH2 CHZCHNHFO PHTHALIMIDE GROUPS I Walter Horstmann, Cologne-Buchheim, and Edgar Siegel, CH3

Leverkusen, Germany, assignors t0 Farbenfabriken CH2CH2GH2 S CH2CH2CH2 Bayer Aktiengesellschaft, Leverkusen, Germany, a cor- 5 ti f G CH2CH2CH2-NCH2CH2CH2 N0 Drawing. Filed Dec. 19, 1966, Ser. No. 602,529 (3113 Claims priority, application Germany, Dec. 28, 1965,

F 48,022 H2c-H2c -cH2-om, H2C- CHz- Int. Cl. C09b 43/00, 43/12 10 U.S. Cl. 260-157 13 Claims N02 H2C CH2, -HzC--CH:- ABSTRACT OF TI'IE DISCLOSURE I Azo dyestuffs having the formula 15 CH:

RHNO C ([)H H? CONH-R N N=N- /C C Q N A N (m E E com in which R denotes identical or different, optionally substituted aromatic or heterocyclic radicals, the radicals H2C 1 H2C"" OH2 X are identical or different substituents, m denotes in- I tegers from 0 to 3 and A is an aliphatic radical which CH2- may be interrupted by hetero atoms or by optionally substituted aromatic radicals. The dyestuffs have good tinctorial strength, thermal stability, fastness to solvents,

light and migration, and are suitable for coloring plastics,

lacquers, or papers and for producing printing colors and -H2CSO2CH2 pigment pastes.

H2C cH2-om DISCLOSURE 40 The object of the present invention comprises valuable new azo dyestuiis which are free from sulphonic acid groups and correspond to the general formula RHN-0C OH HO ClJONH-R U /N-A-N com ff if (20m in which R denotes identical or different, optionally sub- 65 The radicals R can be monoor polynuclear, radicals stituted aromatic or heterocyclic radicals, the radicals f the hfinlehe and naphthalene Series being Preferred- X are identical or diiferent substituents, m denotes in- In this cohteXt there y be mentioned, for p the tegers from 0 to 3 and A is an aliphatic radical which following radicals? P y 0f 4-m hylphenyl-l; may be interrupted by hetero atoms or by optionally 0r 0f P y 0f 4-lhethoXyphehylsubstituted aromatic radicals. 1; yp y Suitable radicalsAare, for example: 1 2 3 11 1 1 g l'aj ig f lil li i 3? -h of gniro-p eny-; -1me y-p eny- -1met ox TCHQCH? TCHQCHZCHETCHZCHT CH2CH2OH2CH2 chlorophenyl-l; 2,5-dirnethoxy 4 chlorophenyl-l; 2-

0 a methyl-S-chlorophenyl- 1 2,5 dimethoxy-phenyl- 1 naph- CH(CH) CH -01; CH thyl'l oil-2' 2 2 2 2 Suitable substituents X are, for example: lower alkyl, such as methyl and ethyl substituents, nitro substituents, CHzCH2, lower alkoxy, such as methoxy or ethoxy substituents,

chloro, fluoro, bromo, methyl-sulphonyl, phenyl-sul- 3 phony], trifluoromethyl substituents, and carbalkoxy, such as carbomethoxy and carbethoxy substituents.

A group of particularly valuable dyestufi's Within the scope of the products of the formula (1) corresponds to the formula -CH (CH CH or an araliphatic radical; the dyestufls are free from sulphonic acid groups.

The new azo dyestuffs of the Formulae I and Ia are obtained, when azo compounds of the formula in which R, X and m have the same meaning as above, or azo compounds of the formula EOH in which R R and R have the same meaning as above, or functional derivatives of these dicarboxylic acids, especially the monoand diesters, monoor diamides, dicarbonimides or -anhydrides, are reacted with aliphatic diamines of the general formula H N--A-NH in which A has the same meaning as above,

(Ila) (III) in a molar ratio of components (II) or (Ila) to component (III) of approximately 2: 1, in the presence of acidic condensation agents, the components being so chosen that the final dyestulfs are free from sulphonic acid groups.

The reaction of the starting components is preferably carried out in a high-boiling organic solvent or solvent mixture, but the components themselves may also act as organic solvents.

The condensation is carried out at an elevated temperature, generally in the range from 80 to 240 C., preferably between 120 C. and 180 C.

The monoazo compounds of the Formulae II and Ha are obtained in known manner by diazotising the optionally substituted 3-amino-phthalic acids or their funcitonal derivatives and coupling with Z-hydroxy-naphthoic acid-(3)-arylides, the components being free from sulphonic acid groups.

The following diazo components can be used for preparing the azo compounds (II) and (Ila), for example: 3-amino-phthalic acid, 3-amino-phthalic acid mono and diesters, such as 3-amino-phthalic acid monomethyl ester( 1) or 3-amino-phthalic acid dimethyl ester, 3-amino 6-methyl-phthalic acid, 3-amino-5-methyl-phthalic acid, 3- amino-5-nitro-phthalic acid, 3-amino-6-nitro-phthalic acid, 3-amino-6-methoxy-phtha1ic acid, 3-arnino 6 chlorophthalic acid, 3-amino-4-methoXy-phthalic acid, 3-amino- 6-bromo-phthalic acid, 3-amino-6-fl-uoro-phthalic acid, 3- amino-6-trifiuoromethyl-phthalic acid, 3-amino-5-trifluoromethyl-phthalic acid, 3 -amino-5,ddimethoxy-phthalic acid, 3-amino-4,5,6-trimethoxy-phthalic acid, 3-amino-5,6- methylenedioXy-phthalic acid, 3-amino-5-cyano-phthalic acid, 3-amino-6-cyano-phthalic acid, 3-amino-5-methoxy-6-ethoXy-phthalic acid, 3-amino--methylsulphonylphthalic acid, 3-amino-4-methy1-phthalic acid, S-amino-S- carbethoxy-phthalic acid, 3-amino-6-carbethoXy-phthalic acid.

(") IIIHz COOH / COOH O I As coupling components for the synthesis of the monoazo compounds (II) and (11a), there may be used, for example: Z-hydroxy-naphthoic acid-(3)-anilide, Z-hydroxy-naphthoic acid-(3) (2-methoxy-)-anilide, Z-hydroxy-naphthoic acid-( 3) (4'-methoXy-)-anilide, 2-hydroxy-naphthoic acid-(3)-(2'-methyl)- anilide, Z-hydroxynaphthoic acid-(3)-(4-methyl)-anilide, Z-hydrOXy-naphthoic acid-(3)-(2',4'-dimethy1-anilide, Z-hydroXy-naphthoic acid-(3-(2-chloro)-anilide, 2-hydroxy-naphthoic thoie acid-(3 (2'-chloro)-anilide, Z-hydroxy-naphthoic acid-(3)-(4'-chloro)-anilide, Z-hydroxy-naphthoic acid- (3 2-chloro-4'-methoxy) -anilide, 2 hydroxy-naphthoic acid-(3)-(2'-methyl-4-chloro)-anilide, 2 hydroXy-naphthoic acid-(3) (2'-methyl-5'-chloro)-anilide, Z-hydroxynaphthoic acid-(3) (2,4'-dimethoxy-5'-chloro)-anilide, 2-hydroxy-naphthoic acid-(3) (2',5'-dimethoxy-4'-chloro)-anilide, Z-hydroxy-naphthoic acid-(3)-(2-methyl-4- methoXy)-anilide, 2 hydroXy-naphthoic acid (3)-(2'- methyl-3'-chloro)-anilide, 2-hydroXy-naphthoic acid-(3)- (2',3',4',5,6' pentaehloro)-anilide, Z-hydroxy-naphthoic acid-(3) [naphthyl(l)] amide, Z-hydroxy-naphthoic acid-(3) [naphthyl(2)] amide, Z-hydroxy-naphthoic acid- 3 2,4'-dimethoxy -anilide, Z-hydroxy-naphthoic acid-(3)-(2-ethoXy)-anilide, Z-hydroxy-naphthoic acid- (3)-(4-ethoxy)-anilide, 2-hydroxy-naphthoic acid-(3-(2, 4'-diethoxy)-anilide, 2 -hydroxy-naphthoic acid-(3)-(2- methoXy-5'-methyl)-anilide, 3 methoXy-2-[(2-hydroxy- 3-naphthoyl)-amino]-dibenzofuran.

It is also possible to use the alkyl, aryl, aralkyl monoand diesters, anhydrides or imides of the above substituted phthalic acids. In comparison with the dicarboxylic acids, dicarboxylic acid anhydrides and imides, the esters are in many cases more readily soluble in the high-boiling organic solvents used.

The following diamines (III) are used, for example for the condensation of the azo compounds according to the invention: 1,2-diamino-ethane, 1,3-diamino-propane, 1,4- diamino butane, 1,5-diamino-pentane, 1,6-diamino-hexane, 3,3'-diamine-di-n-propy1 ether, 3,3'-diamino-di-npropyl thioether, N,N-bis (3 amino-n-propyl)-methylamine, 3,3'-diamino-di-n-propylsulphone, 1,4-di-(aminomethyD-benzene, 1,4 di-(aminomethyl)-2-nitrobenzene, 1,4-di-(aminomethyl) 2 chlorobenzene, 1,4-di-(aminomethyl) 2 methoxy-benzene, 1,4 di (amino-methyl) 2 ethoXy-benzene, 1,3 di (aminomethyD-benzene, 4,4-di-(aminomethyl)-diphenyl, 4,4 di (aminomethyl)-diphenyl ether, 4,4-di-(aminomethyl)-diphenylmethane, 4,4-di-(aminomethyl)-diphenyl-sulphone, 1,4- di- (aminomethyl) -naphthalene, 1-aminomethyl-4- fl-aminoethyl) benzene.

For the condensation of the monoazo dyestufis (II) and (Ila) with the diamines (III) in high-boiling organic solvents, there may be mentioned the following solvents boiling above 80 C., for example: benzene, toluene, xylenes, chlorobenzene, 0-, mp-dichlorobenzene, trichlorobenzenes, nitrobenzene, quinoline, glacial acetic acid, cyclohexane, 1,2,3,4-tetrahydro-naphthalene, naphthalene, tetrachloroethylene, di-n-butyl ether, anisole, diphenyl ether, decalin and mixtures of solvents of this type.

Suitable acidic condensation agents are, for example: acetic acid, propionic acid, anhydrous sodium acetate, zinc chloride, ferric chloride, aluminum chloride, hydrochloric acid, sul huric acid and orthophosphoric acid.

The reaction of the dicarboxy-azo compounds (II) or (Ha) or of their functional derivatives with the diamines (III) is carried out in a proportion of approximately 2:1. A slight excess of the components (11) or (Ila) is frequently desirable in order to react the component (III) completely.

Depending on the choice of components (II) or (IIa), symmetrical or asymmetrical dyestuffs of the Formula I can be synthetised.

To prepare the preferred group of dyestuffs of the Formula Ia, a diamine of the Formula III is condensed with an azo-dicarboxylic acid of the Formula Ila under the stated conditions in a ratio of approximately 1:2.

The products obtained according to the present process are barely soluble to insoluble in water. They are valuable pigment dyestuffs the shades of which are predominantly in the yellow-red to bluish red range. The dyestuffs are in part obtained in the amorphous state but predominantly in crystalline form. They are characterised by a very good tinctorial strength, thermal stability, fastness to solvents, light and migration, and are therefore suitable for colouring plastics, lacquers, or papers and for producing printing colours and pigment pastes.

Due to their excellent thermal stability, the products are especially suitable for colouring polyvinyl chloride and for colouring acrylonitrile-butadiene-styrene copolymers. They are still stable at temperatures of 200 C. and above.

Belgian patent specification No. 652,251 describes pigment dyestuffs of the general structure in which K is defined as the radical of any coupling component, A as an aromatic or heterocyclic system and R as a bivalent alkyl, aryl, aralkyl or hetero radical.

The patent specification, however, does not contain a single example of a dyestufi of the general formula there stated, and not even an example of only one of the components K, A and R The patent specification otherwise contains only a few, very general statements regarding processes for the production of the pigment dyestuffs.

In the following examples the parts are parts by weight; the temperatures are given in degrees centigrade.

Example 1 90 parts 3-amino-phthalic acid are suspended in 1500 parts of water, 162 parts of concentrated hydrochloric acid are added and the mixture is diazotised at 0-5 with a solution of 34.2 parts sodium nitrite in 200 parts of water. The excess nitrile is removed by means of aminosulphonic acid.

152 parts 2 hydroxy-naphthoic acid-(3)-4-ethoxyanilide are suspended in 320 parts ethanol, 21 solution of 80 parts caustic soda in 200 parts water is added, 500

parts ice are thrown in and the mixture is coupled at 5-15 with the above diazo suspension by adding the latter in portions to the coupling mixture. Stirring is continued at 10-15 for 2-3 hours, the mixture is then acidified with 10% hydrochloric acid, suction-filtered, the filtrate is washed with water until free from acid and dried n a drying cabinet at The yield amounts to 220 parts of azo d yestuff.

For conversion into the anhydride, the dry powdered dyestutf is suspended in 1000 part-s chlorobenzene, parts acetic anhydride are added and the mixture is heated at 100-110 for 4 hours. The product is filtered off with suction at 20 and rinsed with benzine. The yield of monoazo-o-dicarboxylic anhydride amounts to 180 parts.

10 parts of this anhydride are suspended in 500 parts o-dichlorobenzene, 50 parts glacial acetic acid and 0.60 part ethylene-diamine are added and the mixture is heated at 140 for 25-30 hours. The precipitated pigment is filtered oil with suction at 60-70", washed with hot o-dichlorobenzene and dried in a vacuum at 80 until the weight remains constant. The yield amounts to 9.2 parts of the pigment dyestuff of the constitution The pigment dyestuif prepared in the manner described above has a good tinctorial strength and a very good fastness to light, lacquer coating and migration.

Example 2 132 parts 3-amino-phthalic acid are suspended in 2300 parts of ice water, 245 parts of concentrated hydrochloric acid are added and the mixture is diazotised at 0-5 with a solution of 50.3 parts sodium nitrite in 200 parts of water. The excess nitrite is destroyed by means of amidosulphonic acid.

205 parts 2 hydroxy-naphthoic acid-(3)-(2'-methyl)- anilide are suspended in 300 parts ethanol, a solution of parts caustic soda in 350 parts water is added, 400 parts of ice are thrown in, and the above diazo suspension is introduced in portions at 5-10 into the coupling mixture thus prepared. Stirring is continued at 10-15 for 2-3 hours, the reaction mixture is adjusted to pH l-2 by the addition of dilute hydrochloric acid, the precipitated azo dyestuif is filtered off with suction, washed with water until free from acid and dried at 80. The yield amounts to 320 parts monoazo-o-dicarboxylic acid. M.P. 298-300.

9.60 parts of this dyestuff are suspended in 500 parts o-dichlorobenzene, 50 parts glacial acetic acid are added and the mixture is heated at -130" for 4 hours. 1.16 parts hexamethylene-diamine are then added and heating is continued at for 25 hours. The precipitated pigment is isolated at 60-70, washed with a little warm o-dichlorobenzene and dried in a vacuum at 80 until the weight remains constant. 9.3 parts of a dyestuif are thus obtained which is bluish-red when diluted and has an excellent tinctorial strength.

Example 3 10.0 parts of the azo dyestuff obtained from 3-aminophthalic acid and 2 hydroxy-naphthoic acid-(3)42- methoxy)-anilide (for preparation of. Examples 1 and 2) are suspended in 950 parts chlorobenzene, 50 parts glacial acetic acid are added and the mixture is heated at 120 for 3-4 hours. 1.36 parts 1,4 di-(aminomethyl)-benzene are then added and heating is continued for 25 hours under gentle reflux. The pigment is filtered off with suction at 60-70", washed with 100 parts chlorobenzene at 60- 70, and dried in a vacuum at 80 until the weight reby following the procedure described in these examples mains constant. 10.0 parts of a red pigment dyestuff are but using, instead of the diazo component, coupling comobtained.

ponents and diamines there stated, the diazo, coupling Very valuable red pigment dyestuffs are also obtained and diamine components compiled in the following Table.

Diazo component Coupling component Diamine B-amino-phthalic acid 2-hydIo xy-naphth0ie acid (3)-(2'-meth- 1,2-diamino-ethane.

D0 4,4di-(aminomethyD-diphenylmeth- Do do Li cl laminobutane.

do 1,4-di-(aminomethyD-benzene. --do... 3,3'-dlamino-di-n-propyl ether. -do. 4,4-di-(aminomethyD-diphenylethgr. Do 2'hydroxy-naphthoic acid(3)-(4-eth- L-diamino-butane.

oxy)-anilide. Do ..do 3,3-diamino-dl-n-propyl ether. Do... do. lA-dl-(aminomethyD-benzene. D0 "d0 1,4-(11-(aminomethyl)-3-methyl-b zene. Do ..do l-eminomethyM(fl-amlnoethyl)- benzene. Do 2-hydroxy-naphthoic acid(3)-(2,5-di- 1,2-diamin0-ethane.

methoxy-4'-ehloro)-ani1lde. Do do 1,4-diamlno-butane. Do .do... 3,3'-diamino-d1-n-propyl ether. Do". .do..- 1,4-di-(aminomethyl)-benzene. Do --do 1,4-(11-(aminomethyl)-3-methyl-b zene. Do ..d0 4,4-di-(amlnomethyl)-dtpheny1. D0 ..d0 N,N- blS-(3-9m1n0-n-pr0pyl)-methylamine. Do 2-hydroxy-naphthoie ac1d-(3)-(3'-ni- 1,2-diam1n0-ethane.

tro)-anilide. Do do 1,4-cli-(eminomethyl)benzene. Dom -..do. 3,3-diamino-di-n-pro yl ether. Do -.do 4,4'-di-(amin0methy1 -diphenylmeth- 8H8. D0 0 4,4'-dl-(aminomethyh-diphenyl ether. Do Z-hydroxy-naphthoic acld-(3)-(2- 1,2-diamino-ethane.

methoxy)-anillde. D0 ..d0 1,4-diamlno-hutane. Do... do... 1,6-dieminohexane. Do... .do... 4,4-di-(aminomethyl)diphenyl. do 3,3-dia.ml.no-di-n-propyl ether. Do... 2-hydroxy-naphthoic acid-(3)-anilide 1,2-diamino-ethane. .....do 1,4-di-(eminomethyD-benzene. D0... 3,3-diarnlno-di-n-propyl ether. D0 d0 4, "di-(amlnomethyl)-diphenylmethme. Do "do 4,4-dl-(anfinomethyD-diphenyl ther. Do Z-hydroxy-nephthoic ac1d-(3)-(4'- 1,2-diam1noethane.

meth0xy)-anilide. Do .-d0 lA-diamino-butam. Do... -..do 1,4-di-(aminomethyD-benzene. -do. LA-di-(eminomethyD-diphenyl. Dom d0 3,3-diamin0-di-n-prepyl ether. Do 2-hydroxy-naphthoic acld-(3)(4- 1,2-diamino-ethane.

methyD-anilide: Do .do 1,4-di-(aminomethyD-benzene. Do. do. 3,3'-diamjno-di-n-propyl ether. DQ ..-d0- 4,4-di(aminomethyD-diphenyl ether. Do --do '-d -(amlncmethyl)-dlpheny1mathene. D0 2-hYdr0xy-naphthoic ac1d-(3)-(4-ehlo- 1,2-diamino-ethane.

ro)-anilidea Do .410 1,6-diamino-hexane. Do". do. 1,4-di-(aminomethylybenzene. ...do. 4,4'-di-(aminomethyD-diphenyl. do 3,3'-diamin0-di-n-propyl ether. Do Z-hydroxy-naphthoic acld- (3) -[naph- 1,2-diamino-ethane.

thy1-(2)]-amide.

do 1,4-diamin0-butane.

1,4-di- (aminomethyD-benzene. 1 4,4-di-(aminomethyh-diphenyl. Do 2-hydr0xy-naphtho1c aeid-(3)-(2,4'- 1,2-dlamjno-ethane,

di ethoxy-5-chloro)-anilide. D0 .410 LE-diamino-hexane. D0 "d0 1, -dl-(amlnomethyl)-3-methyl-b zene. D0 4,-1 d1-(aminomethyn-di henyl m do 3,3'-diamino-di-n-propy1other. Do Z-Mdroxy-naphthoic acld-(3)-(2'- 1,2-dlammo-ethane.

methyl-3'-ehloro)-ani1lde. D0 -.d0--.. LMIaminG-Ixemne.

1,Mi-(emlnomethyD-benzene.

.- 4,4'-dl-(aminomethyD-diphenyl.

Do ..d0 4,4'-dl-(am1n0methyl)-diphenylmeth 8110. D0 ..d0 4,4-di-(aminomethyD-diphenyl ether, Do d0 3,3'-diamin0-dl'n-pr0py1 ether. Do 2-hydroxy-naphthoic aeid-(3)-(2- 1,2-diamino-ethane. methy1-4-methoxy)-an11ide. D0 --d0 1,4-diam1no-butene.

Do.. ..do 1,6-diam1no-hexane.

2-hydroxy-naphthoic acld-(3)-(2'-eth- 1,2-diam1no-ethane.

oxy)-anilide.

Do do 1,6-diamino-hexene.

-. -do 1,4-d1-{ammomethyD-henzene.

Z-hydroxy-naphthoic acid-(3)-(3',5'- 1,2-diam1no-ethene.

dlmethyD-anlllde.

D0 do 1,4'dtamino-butane.

Do .--do 3,3-diamin0-dl-n-propyl ether;

2-hydroxy-naphthoie acid-(3)(2,3'-di- 1,2-diamino-ethane.

methyl)-anilide.

Diazo component Coupling component Diamine Do 2-hydroxy-naphthoic acid-(3)-(2- Do,

methyl-4-chloro)-anilide. Do 2-hydroxy-naphtholc acld-(3)-(2- Do. methoxy--chloro)anilide. Do 2-hydroxy-naphthoic acld-(3)-(2- Do.

methoxy-4-chloro-5-methyl)anillde. 2-hydroxy-naphthoic acid(3)-(2- D0.

methyl-5-chloro)-anilide. Do Z-hYdIOX -naphthoic acid-(3)-(2,4- Do.

dlmethyD-anilide. Do 2-hydroxy-naphthoic acid-(3)-(2,5- Do.

dlmethoxy)-an1llde. Do Z-hydroxy-naphthote acid-(3)-[naph- Do. thyl-(1)]-am1de. Do Z-hYdIOXy-naphthoic acid-(3)(4'- 1,4-diaminobutane.

acetylamino)-anilide. Do do 1,6-diaminohexane: Do 5-[2-hydIoxy-naphthoyl-(3)-am.tno]- 1,2-diamino-ethane.

benzimidazolone.

d0 1,4-diamlno-butane. Do 1,6-diamino-hexane; Do hydroxy-naphthoic acid-(3)-(4'-ben- 1,2-diamino-ethane.

zoylamino)-an1llde. Do -d0 1,6-diamlno-hexane. B-BmIno-G-methoXy-phthalic 2-hydroxy-naphthoic acid(3)-anilide 1,2-dlamino-ethane.

acid.

Do 2-hydroxy-naphthoic acid-(3)-(4-eth Do;

oxy)-anilide. Do 2-hydr0xy-naphthoic acid-(3)-(4- Do.

chloro)-anilide. Do 2-hydIOXy-naphthole acld-(3)-(2'- D0. methyD-anilide. Do 2- YdIOXy-naphthoic acid-(3)42 Do, methyl-4methoxy)-anilide. 3-amino-6-chloro-phthalic acid- Z-hydroxy-naphthoic acid-(3)-anilido. D0. D0... 2-hydroxy-naphthoic acid-(3)-(2- Do. methyD-anilide. Do 2-hydroxy-naphthoic acld-(3)-(4- Do. ethoxy)-anilide. Do 2-hydroxy-naphthoic actd-(3)-(2-eth- Do.

oxy)-anilide. 3-aminc-4-chlorophthallc acid 2-hydroxy-naphtholc aeid-(3)-anilide. Do. Do Z-hydroxy-naphthoie acid-(3)-(4- Do. chloro)-anilide. Do 2-hydroxy-naphthoic acid-(3)-(2- Do.-

methyl-4-methoxy)anilide. Do Z-hydroxy-naphtholc acid-(3)-(2'- Do. methyD-anllide. 3-amino-4,5-dich1orophthalie 2-hydroxy-naphth0ic acid- (3) anilide- Do.

acid.

Do 2-hydroxy-naphthoic acld-(3)-(2- Do. methyD-anillde. Do Z-hydroxy-naphtholc acid-(3)-(4- Do. ethoxy)-anillde. S-amlno-B-methyl-phthalic 2-hydroxy-naphthoio acid- (3) anilide Do.

acid.

Do 2-hydroxy-naphthoic acld-(3)-(2- Do. methyl)-anllide. Do 2-hydr0xy-naphthoic acld-(3)-(4'- Do. ethoxy)-anilide. D0 2-hydroxy-naphthoic acid-(3)-(4- Do. ch1oro)-anlllde;

Example 4 Example 6 50 10 parts of the anhydride of the dyestufl which is obtained by coupling diazotised 3-amino-phthalic acid with 2-hydroxy-naphthoic acid-(3)-4'-ethoxy-anilide and 1.16 parts of 1,6-diamino-hexane are heated for 5 hours at 120130 in a mixture of 250 parts p-xylene and parts glacial acetic acid. The precipitated pigment is filtered off with suction at 60-70, washed with hot p-xylene and dried at 100 in a drying cabinet. The yield amounts to 8.2 parts of pigment dyestufi which has a very good fastness to light.

Example 5 10.5 parts of the dyestuff obtained from diazotised B-amino-phthalic acid and Z-hydroxy-naphthoic acid-(3)- 2-ethoxy-analide and 9.6 parts of the dyestutf obtained from 3-amino-phthalic acid and 2-hydroxy-naphthoicacid-(3)-anilide are heated for minutes at 120 in a mixture of 450 parts o-dichlorobenzene and parts glacial acetic acid and 1.2 parts ethylene diamine added subsequently. After heating for 2 hours at 120 the mixture is cooled at -70, the precipitated pigment is filtered off with suction, washed with 200-300 parts o-dichloro-benzene and dried at 100 in a vacuum until the weight remains constant. 16.8 parts of pigment are thus obtained. This mixture of the three possible disazo dyestuffs has a good fastness to light and lacquer coating.

20 parts of the azo dyestutf obtained from diazotised 3amino-6-methoxy-phthalic acid and Z-hydroxy-naphthcic-acid-(3)-anilide are heated for 30 minutes at 130 in a mixture of 450 parts nitrobenzene and 50 parts propionic acid. 2.64 parts 3,3'-diamino-di-n-propyl-ether are then added and the mixture heated for further 4 hours at 120-130. The precipitated pigment is filtered 06 with suction at 50-60", washed with warn nitrobenzene and subsequently with methanol, and dried. The yield amounts 0 to 17.3 parts of the pigment dyestutf of the constitution Example 7 10.7 parts of the azo dyestutf obtained from diazotised 3-arnino-phthalic-acid and 2-hydroxymaphthoic acid-(3)- (4'-acetylamino)-anilide are heated for 30 minutes at 75 120 in a mixture of 220 parts o-dichlorobenzene and 30 parts glacial acetic acid. 0.6 part of ethylendiamine is then added and the mixture heated for further 3 hours at l20-l30. The precipitated pigment is filtered olf with suction at 6070, washed with o-dichlorobenzene and dried in a vacuum at 80 until the weight remains constant. The yield amounts to 9.8 parts of the pigment dyestufi? of the constitution The pigment dyestutt has a good fastness to light and migration.

Example 8 in which R is phenyl or naphthyl or phenyl or naphthyl substituted with methyl, chloro, methoxy, ethoxy or nitro; X is lower alkyl, lower alkoxy, nitro, chloro, fluoro, bromo, methyl-sulphonyl, phenyl-sulphonyl, trifluoromethyl or carbalkoxy; m is a number from to 3; and A is a saturated aliphatic hydrocarbyl chain, or a saturated aliphatic hydrocarbyl chain containing in the chain linkages of --0, S-, NCH S0 diphenylene, diphenylene oxide, diphenylene sulphone, diphenylene methane, stilbene, phenylene, or phenylene substituted with nitro, chloro, methoxy or ethoxy on the ring.

2. A20 dyestulf free from sultonic acid groups and corresponding to the formula in which R is hydrogen, nitro, methyl, methoxy, ethoxy, or chloro; R is hydrogen, methyl, methoxy, ethoxy or chloro; R is hydrogen or chloro; and A is a saturated aliphatic hydrocarbyl chain, or an aliphatic hydrocanbyl chain containing in the chain linkages of O--, -S, NCH S0 diphenylene, diphenylene oxide, diphenylene sulphone, diphenylene methane, stilbene, phenylene, or phenylene substituted with nitro, chloro, methoxy or ethoxy on the ring.

3. A20 dyestuif free from sulphonic acid groups according to claim 2, in which A stands for a member selected from the group consisting of 1,2-ethylene, 1,3- propylene, 1,4-butylene, 1,5-pentylene and 1,6-hexylene radicals and stands for a member selected from the group consisting of phenyl, 2-methyl-phenyl-l, 3-methyl-phenyl-l, 4-methylphenyl-l, 2-chloro-phenyl-1, 3-chloro-phenyl-l, 4-chlorophenyl-l, Z-methoxy-phenyl-l, 3-methoxy-phenyl-1, 4-methoxy-phenyl-l, 2-nitro-phenyl-l, 3-nitro-phenyl-1, 4-nitrophenyl-l, 2-eth0xy-phenyl-l, 3-ethoxy-phenyl-1, 4-ethoxyphenyl-l, 2-methyl-4-chloro-phenyl-l, 2,5-dimethoxy-4- chloro-phenyl-l, 2,4-dimeth0Xy-S-chloro-phenyl-1, naphthyl-l and naphthyl-2.

C ONE-R 5. The dyestulf of the formula mom-Qmr-oo on 13 6. The dyestufi of the formula 11. The dyestuflf of the formula NH-O C 7. The dyestuff of the formula 10. The dyestuff of the formula 222 L 555 5 L4 1 0 66 222 2 2 s I s T u 1 N L r s, E n m 8 m A n B WP m R s mmu E X H e c o m m m m m a u mT m m SFSH n 2 e P R D 078 F E 666 L O T999 E 1 nna G mun 1 n 1 H ,5 826 D M 376 ,1. D L mm Y 14 m 44 0 233 F 82 u 0 m w 6 9 fillllllzlllJ H J N 0 ll ml N H O 0 w H N N C N 0 H |||ll| 

